CN104991008B - Method for measuring content of silane compound by gas chromatographic method - Google Patents
Method for measuring content of silane compound by gas chromatographic method Download PDFInfo
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- CN104991008B CN104991008B CN201510449554.4A CN201510449554A CN104991008B CN 104991008 B CN104991008 B CN 104991008B CN 201510449554 A CN201510449554 A CN 201510449554A CN 104991008 B CN104991008 B CN 104991008B
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Abstract
The invention provides a method for measuring the content of a silane compound by a gas chromatographic method. The method includes the following steps: a capillary chromatographic column, an automatic sample injection bottle, a liner tube, an automatic sample injection needle, a sample injection port isolation pad and a graphite pad are selected; all the components are connected and mounted; a sample is injected into the automatic sample injection bottle and put into a sample injection plate, and a simple random sampling mode is a three-layer interlayer mode; a chromatograph chart is integrated, an area normalization method is adopted, all peaks having the peak height larger than three times of a noise level are integrated, and the percentage of the area of the peaks accounting for the total peak area is calculated, wherein the percentage is the percentage of the silane compound main content accounting for the whole matrix. The method provided by the invention can reduce the interference of impurities in the sample and the interference of exogenous impurities, so as to improve the accuracy degree of accurate quantification of the silane compound main content through the gas chromatographic method.
Description
Technical field
The invention provides a kind of content assaying method detecting the main content of silane coupler in chemicals, it is particularly well-suited to
The detection of detection TMOS class chemical combination owner's content.
Background technology
In recent years with the rapidly growth of domestic market demand, China's silicone rubber industry development is rapid, and silicone rubber has excellent
Different high-low temperature resistant, weather-proof, hydrophobic, electric insulating quality, physiological inertia, nontoxic, tasteless, corrosion-free the features such as, electronic apparatus,
The fields such as health care, industrial or agricultural, defence and military have a wide range of applications, and wherein silane compound is exactly a kind of novel silicon rubber
The cross-linking agent of glue.Therefore the detection research to the main content of silane compound has great significance.
It is to the domestic detection method to the main content of silane compound has carried out substantial amounts of research up till now.But mesh
Front analysis method can not will be completely separable to impurity all of in silane compound matrix and main content, therefore to main content
Analysis has a great impact.Silane compound body is extremely complex, and this product creates a large amount of in producing building-up process
By-product and raw material reaction not exclusively wait impurity pollution, and this Product Activity is extremely strong, is easy to absorption in atmosphere
Moisture hydrolyzes, and produces other impurities material and brings very big impact to its main content, so how to reduce the interference of impurity, accurately
The main content of detection silane compound be a vital problem.
Content of the invention
The invention provides a kind of survey of the detection main content of silane compound simple to operate, reproducible, high precision
Determine method, the method can reduce the interference of impurity and exogenous impurity in sample, thus improving gas chromatography accurate quantitative analysis
The accuracy of the main content of silane compound.
Realizing the technical scheme that above-mentioned purpose of the present invention adopted is:
A kind of method of the content detecting silane compound with gas chromatography, comprises the following steps:
(1), choose the capillary chromatographic column of 5% phenyl -95% methyl polysiloxane filler, auto injection bottle, bushing pipe, from
Dynamic sample introduction needle, injection port dottle pin and graphite pads, each part are attached installing, and can detecting system normal works；
(2), setting sampling volume is 0.2ul, split sampling, and split ratio is 50:1；Carrier gas is nitrogen；Post stream mode is perseverance
Stream mode, flow is 1.0ml/min；The temperature of injection port is 280 DEG C, and dottle pin purge mode is standard, and purge flow rate is
3.0ml/min；Flame ionization ditector temperature is 280 DEG C, and hydrogen is respectively 30ml/min, 400ml/ with the flow of air
min；Tail wind drift amount is 25ml/min；The heating schedule of post phase is: 110 DEG C of initial temperature, keeps 2min, and heating rate is 20
DEG C/min, 260 DEG C of final keeping temperature, keep 6min；
(3), treat the injector temperature of instrument, the temperature of detector, column flow, the flow of purge flow rate, hydrogen and air,
Tail wind drift amount, the background response value of flame ionization ditector reach setting value stable equilibrium；
(4), sample disposable syringe is drawn and crossed organic faciess film, inject in auto injection bottle and put into sample injection disc
In；
(5), before sample introduction, sample introduction needle is first cleaned successively with normal hexane and acetone, and sample introduction needle is entered with sample before extracting sample again
Row rinse, Sampling Modes are three layer interlayer patterns, and after sample introduction, sample introduction needle normal hexane and acetone clean successively；
(6), chromatogram is integrated, using area normalization method, the peak that all peak heights are more than 3 times of levels of noise is all carried out
Integration, calculates the percentage rate that above peak area accounts for total peak area, the as main content of silane compound accounts for the hundred of whole matrix
Divide ratio.
Bushing pipe described in step (1) be glass bushing pipe and pass through deactivation process in be filled with a small amount of glass cotton shunt and regardless of
Flow universal bushing pipe；Described auto injection bottle is the auto injection bottle of 1.5ml；Described auto injection gauge is 10ul；Institute
State injection port dottle pin from using the pure silica gel material of ultralow loss, 400 DEG C of heatproof, the dottle pin of low-bleed；Graphite pads are selected resistance to
By 350 DEG C of graphite grazing pad.
Three layer interlayer patterns described in step (5) are particularly as follows: sample introduction needle first takes out 1ul air, then extract 0.2ul sample,
Finally extract 1ul air, repeat three times.
Compared with prior art, the invention has the advantages that adopting direct injection analysis in the 1, present invention, with its other party
Method adds the method that solvent sample dissolution enters conformal analysis again to compare, and eliminates the impurity interference to be come of a large amount of solvents and solvent to sample
The impact that product produce, thus the spectrogram obtaining is cleaner, substantially reduces the assay of the main content to sample for the impurity
Impact.Do not sample in the present invention any reagent, there is no any pollution to environment, it also avoid operator's contact poisonous molten
Agent produces harm to human body, due to not having the impurity that reagent brings to decrease the pollution to instrument and capillary chromatographic column for the impurity,
So that the care and maintenance of instrument is easier, therefore also in certain degree, protect instrument.
2nd, in the present invention, sample introduction type is 3 layer interlayer sample introductions, because the type sample has certain viscosity, so entering original mold
Formula selects 3 layer interlayer sample introductions, which reduces sample in sample introduction because viscosity large sample may have a small amount of part residual
In sample introduction needle, so that sample is reproducible.
3rd, the present invention adopts gas chromatographic analysiss, using the capillary chromatography of (5%- phenyl)-methyl polysiloxane filler
It is filled with a small amount of glass cotton shunting universal with regardless of flowing in post, the dottle pin of high temperature resistant low-bleed and graphite grazing pad, deactivation process
Bushing pipe；Sampling volume is 0.2-0.5ul, shunting or not shunt mode (practical situation according to instrument and sample feeding volume Lai
Determine whether to shunt)；Nitrogen makees carrier gas；It is 0.5-1.2ml/min using constant current mode flow velocity；The temperature of injection port is 250-
300 DEG C, dottle pin purge mode is 2-5.0ml/min for standard purge flow rate；The temperature of detector is 250-300 DEG C, tail wind drift
Measure as 20-30ml/min；The heating schedule of post phase: initial temperature 90-120 DEG C, keep 1-3min, heating rate be 15-25 DEG C/
Min, final keeping temperature 240-270 DEG C, keep 5-10min.Make all of impurity and main content in silane compound matrix
Completely separable.
4th, the application adopts area normalization method to process obtained chromatogram, because the impurity of silane compound is in hydrogen
Response value on flame ionic detector is essentially the same, therefore response factor is 1, and instrument can directly calculate silane compound
Main content peak area accounts for the percentage rate of total peak area, and that is, the main content of silane compound accounts for the percentage ratio of whole matrix, such energy
Intuitively reflect very much the percentage ratio of the matrix shared by main content of sample.
Specific embodiment
With reference to specific embodiment, detailed specific description is done to the present invention, but protection scope of the present invention not office
It is limited to following examples.
Embodiment 1
In the present embodiment, propyl group triacetoxysilane sample shakes up rear direct injected and repeats 5 parallel surveys
Fixed.Specific operation process is as follows:
1. inspection apparatus hardware: whether particular exam instrument sample introduction needle blocks, whether sampling system is normal, capillary chromatography
Whether the model of post is correct, whether detecting system is normal.
2. prepare consumptive material during analysis: using the capillary chromatography of (5%- phenyl) -95% methyl polysiloxane filler
The capillary chromatographic column (specification 30m × 0.25mm × 0.25um) of post such as Agilent company db-5, and with aging；Auto injection
The auto injection bottle for 1.5ml for the bottle；Bushing pipe shunt/is not shunted for glass bushing pipe and is filled with a small amount of glass cotton in being processed by deactivation
Shunt and regardless of the universal bushing pipe of stream；Auto injection gauge is 10ul；The dottle pin of injection port is from pure using ultralow loss
Silica gel material, heatproof up to 400 DEG C, the Agilent low-bleed bto dottle pin of low-bleed；Capillary chromatographic column graphite pads select graphite
Sealing gasket can tolerate up to 350 DEG C of high temperature.
3. instrument chromatographiccondition is set: sampling volume is 0.5ul, split sampling, split ratio is 50:1 (split ratio root
It is configured according to sampling volume and gas chromatograph sensitivity)；Carrier gas is nitrogen；Post stream mode is constant current mode, and flow is
1.2ml/min；The temperature of injection port is 300 DEG C, and dottle pin purge mode is standard, and purge flow rate is 5.0ml/min, and bushing pipe is to divide
Stream and the type not shunted；Flame ionization ditector temperature is 300 DEG C, the flow difference 30ml/min of hydrogen and air,
400ml/min；Tail wind drift amount is 30ml/min；The heating schedule of post phase: 120 DEG C of initial temperature, keep 3min, heating rate is
25 DEG C/min, 270 DEG C of final keeping temperature, keep 10min.
4. instrument balance: wait the temperature of injection port of instrument, the temperature of detector, column flow, purge flow rate, hydrogen with
The flow of air, tail wind drift amount, the background response value stabilization balance of flame ionization ditector..
5. the process of sample: sample is drawn 1ml with the disposable syringe of 1.0ml and aperture excessively is the organic of 0.22um
Phase film, puts in sample injection disc in the auto injection bottle of injection 1.5ml.
6. sample feeding: first allow instrument run empty needle according to program, observe and see whether instrument instrument pollutes, then carry out sample
Analysis, before sample introduction, sample introduction needle first uses normal hexane and acetone respectively cleaning three times.Carry out three rinses when extracting sample with sample,
Sampling Modes are three layer interlayer patterns, and that is, sample introduction needle first takes out 1ul air, then extracts 0.2ul, finally extract 1ul air repeat into
The speed of row three times and push rod is set at a slow speed, and after sample introduction, sample introduction needle is first cleaned with normal hexane 3 times, then cleans 3 times with acetone.
7. computational methods: the integration of the chromatogram vertical otherwise tangent line integration method of baseline, using area normalization method, owns
The peak of level of noise that the peak height at peak is more than 3 times will integrate, and peak area accounts for the percentage rate of total peak area to draw silanes chemical combination
Owner's content accounts for the percentage ratio of whole matrix.5 times parallel determinations are as shown in table 1:
The repeatability of table 1 sample
Embodiment 2
In the present embodiment, propyl group triacetoxysilane sample shakes up rear direct injected and repeats 5 parallel surveys
Fixed.Specific operation process is as follows:
1. inspection apparatus hardware: whether particular exam instrument sample introduction needle blocks, whether sampling system is normal, capillary chromatography
Whether the model of post is correct, whether detecting system is normal.
2. prepare consumptive material during analysis: using the capillary chromatography of (5%- phenyl) -95% methyl polysiloxane filler
The capillary chromatographic column (specification 30m × 0.25mm × 0.25um) of post such as Agilent company db-5, and with aging；Auto injection
The auto injection bottle for 1.5ml for the bottle；Bushing pipe shunt/is not shunted for glass bushing pipe and is filled with a small amount of glass cotton in being processed by deactivation
Shunt and regardless of the universal bushing pipe of stream；Auto injection gauge is 10ul；The dottle pin of injection port is from pure using ultralow loss
Silica gel material, heatproof up to 400 DEG C, the Agilent low-bleed bto dottle pin of low-bleed；Capillary chromatographic column graphite pads select graphite
Sealing gasket can tolerate up to 350 DEG C of high temperature.
3. instrument chromatographiccondition is set: sampling volume is 0.2ul, split sampling, split ratio is 50:1 (split ratio root
It is configured according to sampling volume and gas chromatograph sensitivity)；Carrier gas is nitrogen；Post stream mode is constant current mode, and flow is
1.0ml/min；The temperature of injection port is 280 DEG C, and dottle pin purge mode is standard, and purge flow rate is 3.0ml/min, and bushing pipe is to go
Live and be filled with a small amount of glass cotton shunting in processing and regardless of the universal bushing pipe of stream；Flame ionization ditector temperature is 280 DEG C, hydrogen
The flow of gas and air 30ml/min, 400ml/min respectively；Tail wind drift amount is 25ml/min；The heating schedule of post phase: initial temperature
110 DEG C of degree, keeps 2min, and heating rate is 20 DEG C/min, and 260 DEG C of final keeping temperature keeps 6min.
4. instrument balance: wait the temperature of injection port of instrument, the temperature of detector, column flow, purge flow rate, hydrogen with
The flow of air, tail wind drift amount, the background response value stabilization balance of flame ionization ditector..
5. the process of sample: sample is drawn 1ml with the disposable syringe of 1.0ml and aperture excessively is the organic of 0.22um
Phase film, puts in sample injection disc in the auto injection bottle of injection 1.5ml.
6. sample feeding: first allow instrument run empty needle according to program, observe and see whether instrument instrument pollutes, then carry out sample
Analysis, before sample introduction, sample introduction needle first uses normal hexane and acetone respectively cleaning three times.Carry out three rinses when extracting sample with sample,
Sampling Modes are three layer interlayer patterns, and that is, sample introduction needle first takes out 1ul air, then extracts 0.2ul, finally extract 1ul air repeat into
The speed of row three times and push rod is set at a slow speed, and after sample introduction, sample introduction needle is first cleaned with normal hexane 3 times, then cleans 3 times with acetone.
7. computational methods: the integration of the chromatogram vertical otherwise tangent line integration method of baseline, using area normalization method, owns
The peak of level of noise that the peak height at peak is more than 3 times will integrate, and peak area accounts for the percentage rate of total peak area to draw silanes chemical combination
Owner's content accounts for the percentage ratio of whole matrix.From chromatogram, noiseless peak in sample, impurity content main with sample separates effect
Really good, peak shape is symmetrical, and signal to noise ratio is high.5 parallel determinations such as tables 2:
The repeatability of table 2 sample
Compared according to the content repeated experiment of embodiment 1 and the main content of embodiment 2 propyl group triacetoxysilane and understand,
Suitable good of the repeatability of embodiment 2 sample.
Claims (4)
1. a kind of method of the content detecting silane compound with gas chromatography, described silane compound is propyl group three
Acetoxylsilane is it is characterised in that comprise the following steps:
(1), choose the capillary chromatographic column of 5% phenyl -95% methyl polysiloxane filler, auto injection bottle, bushing pipe, automatically enter
Sample pin, injection port dottle pin and graphite pads, each part are attached installing, and can detecting system normal works；
(2), setting sampling volume is 0.2～0.5ul, split sampling, and split ratio is 50:1；Carrier gas is nitrogen；Post stream mode is
Constant current mode, flow is 0.5～1.2ml/min；The temperature of injection port is 250～300 DEG C, and dottle pin purge mode is standard, blows
Sweeping flow is 2.0～5.0ml/min；Flame ionization ditector temperature is 250～300 DEG C, and hydrogen is divided with the flow of air
Wei not 30ml/min, 400ml/min；Tail wind drift amount is 20～30ml/min；The heating schedule of post phase is: initial temperature 90～
120 DEG C, keep 1～3min, heating rate is 15～25 DEG C/min, 240～270 DEG C of final keeping temperature keeps 5～10min；
(3), treat that the injector temperature of instrument, the temperature of detector, column flow, the flow of purge flow rate, hydrogen and air, tail blow
Flow, the background response value of flame ionization ditector reach setting value stable equilibrium；
(4), sample disposable syringe is drawn and crossed organic faciess film, inject in auto injection bottle and put in sample injection disc；
(5), before sample introduction, sample introduction needle is first cleaned successively with normal hexane and acetone, and sample introduction needle is moistened with sample before extracting sample again
Wash, Sampling Modes are three layer interlayer patterns, and after sample introduction, sample introduction needle normal hexane and acetone clean successively；
(6), chromatogram is integrated, using area normalization method, the peak that all peak heights are more than 3 times of levels of noise is all amassed
Point, calculate the percentage rate that above peak area accounts for total peak area, the as main content of silane compound accounts for the percentage of whole matrix
Than.
2. according to claim 1 with gas chromatography detect silane compound content method it is characterised in that:
Bushing pipe described in step (1) be glass bushing pipe and pass through deactivation process in be filled with a small amount of glass cotton shunt universal with regardless of stream
Bushing pipe；Described auto injection bottle is the auto injection bottle of 1.5ml；Described auto injection gauge is 10ul；Described injection port
Dottle pin is from using the pure silica gel material of ultralow loss, 400 DEG C of heatproof, the dottle pin of low-bleed；Graphite pads select 350 DEG C of tolerance
Graphite grazing pad.
3. according to claim 1 with gas chromatography detect silane compound content method it is characterised in that:
In step (2), setting sampling volume is 0.2ul, and split ratio is 50:1；Column flow is 1.0ml/min；The temperature of injection port is 280
DEG C, dottle pin purge flow rate is 3.0ml/min；Flame ionization ditector temperature is 280 DEG C；Tail wind drift amount is 25ml/min；
The heating schedule of post phase is: 110 DEG C of initial temperature, keeps 2min, and heating rate is 20 DEG C/min, 260 DEG C of final keeping temperature,
Keep 6min.
4. according to claim 1 with gas chromatography detect silane compound content method it is characterised in that:
Three layer interlayer patterns described in step (5) are particularly as follows: sample introduction needle first takes out 1ul air, then extract 0.2ul sample, finally extract
1ul air, repeats three times.
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| CN106568854B (en) * | 2016-10-14 | 2019-05-21 | 内蒙古神舟硅业有限责任公司 | The measuring method and device of silane contents in a kind of polysilicon tail gas |
| CN114740103B (en) * | 2022-03-16 | 2023-06-23 | 天津键凯科技有限公司 | Polypolidocanol oligomer distribution detection method |
| CN115184511B (en) * | 2022-08-25 | 2023-09-19 | 宜宾五粮液股份有限公司 | Method for in-situ determination of volatile phenolic substances in white spirit |
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| CN102141549B (en) * | 2010-12-27 | 2013-08-21 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Methyltriacetoxysilane analysis and detection method |
| JP5560239B2 (en) * | 2011-07-04 | 2014-07-23 | 信越化学工業株式会社 | Gas chromatography separation method for silane / chlorosilanes and column for gas chromatography |
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